Polyarylene ether sulfones

ABSTRACT

A process for the manufacturing of a poly(arylether sulfone)polymer comprising reacting in a solvent mixture comprisng a polar aprotic solvent and in the presence of an alkali metal carbonate, a monomer mixture which contains: at least one 1,4:3,6-dianhydrohexitol selected from the group consisting of isosorbide (1), isomannide (2) and isoidide (3); at least one dihaloaryl compound of formula (S): X—Ar 1 —SO 2 -[Ar 2 -(T-Ar 3 )n-SO 2 ] m -Ar 4 —X wherein n and m, equal to or different from each other, are independently zero or an integer of 1 to 5; X and X′, equal to or different from each other, are halogens selected from F, Cl, Br, I; each of Ar 1 , Ar 2 , Ar 3  and Ar 4  equal to or different from each other and at each occurrence, is an aromatic moiety, T is a bond or a divalent group optionally comprising one or more than one heteroatom; optionally, at least one dihydroxyl compound different from the diol (AA); optionally, at least one dihaloaryl compound different from the dihalo (BB); and optionally, at least one hydroxyl-halo compound [hydro-halo (A′B′)]; being understood that the overall amount of halo-groups and hydroxyl-groups of the monomers of the monomer mixture is substantially equimolecular, so as to obtain a polymer (b-PAES), wherein the reaction is carried out at a total % monomer mixture concentration equal to or more 10% and less than 70% with respect to the combined weight of monomer mixture and solvent mixture.

This application claims priority to U.S. provisional application No.61/724725 filed on 9 Nov. 2012 and to European application No.12194545.5 filed on 28 Nov. 2012, the whole content of each of theseapplications being incorporated herein by reference for all purposes.

FIELD OF INVENTION

The present invention pertains to novel polyarylene ether sulfonesderived from bio-based feed-stocks, to a process for the manufacture ofpolyarylene ether sulfones derived from bio-based feed-stocks havinghigh molecular weights, and to their use for the manufacture of shapedarticles.

BACKGROUND OF THE INVENTION

The development of renewable bio-based chemicals has the potential toreduce the amount of petroleum consumed in the chemical industry andalso to open new high-value-added markets to agriculture;1,4:3,6-dianhydrohexitols are examples of such chemicals.

Interest in the production of 1,4:3,6-dianhydrohexitols, especiallyisosorbide, has been generated by potential industrial applicationsincluding the synthesis of polymers such as notably polyesters,polyethers, polyurethanes and polyamides. The use of1,4:3,6-dianhydrohexitols in polymers, and more specifically inpolycondensates, can be motivated by several features: they are rigidmolecules, chiral, and non-toxic. For these reasons, there areexpectations that polymers with high glass transition temperature and/orwith special optical properties can be synthesized. Also the innocuouscharacter of the molecules opens the possibility of applications inpackaging or medical devices.

The industrial production of such monomers is a developing area, quicklymaking available this feedstock at more and more attractive prices.Moreover, interest in chemicals derived from renewable resources isincreasing and becoming a decisive argument: as the carbon contained inbioplastics is not derived from fossilized biomass, but from atmosphericCO₂ absorbed by vegetals biomass, these plastics should alleviate theeffects of climate change.

Depending on the chirality, three isomers of the1,4:3,6-dianhydrohexitols sugar diol exist, namely isosorbide (1),isomannide (2) and isoidide (3):

The 1,4:3,6-dianhydrohexitols are composed of two cis-fusedtetrahydrofuran rings, nearly planar and V-shaped with a 120° anglebetween rings. The hydroxyl groups are situated at carbons 2 and 5 andpositioned on either inside or outside the V-shaped molecule, as shownin scheme 1. They are designated, respectively, as endo or exo. Isoididehas two exo hydroxyl groups, whereas for isomannide they are both endo,and for isosorbide there is one exo and one endo hydroxyl group. It isgenerally understood that the presence of the exo substituent increasesthe stability of the cycle to which it is attached. Also, exo and endogroups exhibit different reactivities since they are more or lessaccessible depending on the steric requirements of the studied reaction.The reactivity also depends on the existence of intramolecular hydrogenbonds.

As per the manufacture of these 1,4:3,6-dianhydrohexitols, to summarizebriefly, starch extracted from biomass and in particular from cornstarch, is first degraded into d-glucose (1.A) and d-mannose (2.A) by anenzymatic process. The hydrogenation of these two sugars givesd-sorbitol (1.B) and d-mannitol (2.B); sorbitol and mannitol cansubsequently be dehydrated to obtain isosorbide (1) and isomannide (2),as shown herein below:

Finally, the third isomer, isoidide (3), can be produced from 1-idosefollowing a similar procedure as above sketched, but 1-idose rarelyexists in nature and cannot be extracted from vegetal biomass. For thisreason researchers have developed different pathways to isoidide,including isomerisation of isosorbide or isomannide.

Kricheldorf et al. first reported the preparation and characterizationof poly(ether sulfone)s containing isosorbide from silylated isosorbideand difluorodiphenylsulfone (DFDPS) in 1995 (H. Kricheldorf, M. AlMasri, J. Polymer Sci., Pt A: Polymer Chemistry, 1995, 33, 2667-2671).Since the silylation step adds significant cost, Kricheldorf and Chatti(High Performance Polymers, 2009, 21, 105-118) modified theirpolymerization conditions and reported that poly(ether sulfone)scontaining isosorbide could be made from pure isosorbide and DFDPS. Thehighest apparent molecular weight polymer obtained had an inherentviscosity (IV) of 0.65 dL/g, said IV was measured according to followingconditions: CH₂Cl₂/trifluoroacetic acid solution (9/1 v/v) at 20° C.,0.20 dL/g. The glass transition temperature of this polymer was reportedas 245° C. No examples were described where the polymerization reactionwith isosorbide was conducted with the less reactivedichlorodiphenylsulfone (DCDPS).

There is still a need in the art for an efficient process for themanufacturing of poly(arylether sulfone)s (PAES) polymers comprisingrecurring units derived from bio-compatible and bio-based raw materialsand a variety of dihaloaryl compounds comprising at least one SO₂ group,whereby said (PAES) polymers are characterized by having high molecularweights (Mw); having excellent thermal stability, high stiffness andstrength, good toughness and attractive impact properties; allowing toprovide improved performance relative to current commercial PAES gradesfor applications such as membrane, medical, aerospace, automotiveapplications.

SUMMARY OF INVENTION

The Applicant has now found that it is possible to advantageouslymanufacture poly(arylether sulfone)s (PAES) having high molecular weightcomprising moieties derived from incorporation of1,4:3,6-dianhydrohexitols, said PAES polymers advantageously fulfillingthe above mentioned needs, including excellent thermal stability, andimproved impact properties.

The invention pertains to a process for the manufacturing of apoly(arylether sulfone)polymer [polymer (b-PAES), herein after]comprising reacting in a solvent mixture comprising a polar aproticsolvent and in the presence of an alkali metal carbonate, a monomermixture which contains:

-   -   at least one 1,4:3,6-dianhydrohexitol [diol (AA), herein after]        selected from the group consisting of isosorbide (1),        isomannide (2) and isoidide (3):

-   -   at least one dihaloaryl compound [dihalo(BB), herein after] of        formula (S): X—Ar¹—SO₂—[Ar²-(T-Ar³)_(n)—SO₂]_(m)—Ar⁴—X′ formula        (S)

wherein

-   -   n and m, equal to or different from each other, are        independently zero or an integer of 1 to 5; X and X′, equal to        or different from each other, are halogens selected from F, Cl,        Br, I; preferably Cl or F.    -   each of Ar¹, Ar², Ar³ and Ar⁴ equal to or different from each        other and at each occurrence, is an aromatic moiety.    -   T is a bond or a divalent group optionally comprising one or        more than one heteroatom; preferably T is selected from the        group consisting of a bond, —CH₂—, —C(O)—, —C(CH₃)₂—, —C(CF₃)₂—,        —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—, and a group of formula:

-   -   optionally, at least one dihydroxyl compound [diol (A′A′)]        different from diol (AA), as detailed above;    -   optionally, at least one dihaloaryl compound [dihalo (B′B′)]        different from dihalo (BB), as detailed above;    -   optionally, at least one hydroxyl-halo compound [hydro-halo        (A′B′)]; being understood that the overall amount of halo-groups        and hydroxyl-groups of        the monomers of the monomer mixture is substantially        equimolecular, so as to obtain a polymer (b-PAES),        wherein the reaction is carried out at a total % monomer mixture        concentration [total % monomers, herein after] equal to or more        15% and less than 70% with respect to the combined weight of        monomer mixture and solvent mixture.

As said, the term” total % monomers” is defined as the sum of the weightof all monomers initially present in the monomer mixture in grams,designated as M_(wt), divided by the combined weight of all monomersinitially present in the monomer mixture and of the solvent mixture,wherein the weight of the solvent mixture in grams is designated asS_(wt).

The total % monomers is thus equal to the formula:

100×M_(wt)/(M_(wt)+S_(wt)).

The total % monomers is more preferably at least 20%, even morepreferably at least 25%.

The total % monomers is in general less than 60%, preferably less than50%, more preferably less than 45% and even more preferably les than42%.

Very good results have been obtained at a total % monomers in a rangefrom 25% -42%.

For the purpose of the present invention, the expression “substantiallyequimolecular” used with reference to the overall amount of halo-groupsand hydroxyl-groups of the monomers of the monomer mixture, as abovedetailed, is to be understood that the molar ratio between the overallamount of hydroxyl groups of the monomers of the monomer mixture andoverall amount of halo groups of the monomers of the monomer mixture isof 0.95 to 1.05, preferably of 1.00 to 1.04, more preferably of 1.01 to1.02, good results were obtained with a ratio of 1.02.

The aromatic moiety in each of Ar¹, Ar², Ar³ and Ar⁴ equal to ordifferent from each other and at each occurrence is preferably complyingwith following formulae:

wherein:

-   -   each R_(s) is independently selected from the group consisting        of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether,        carboxylic acid, ester, amide, imide, alkali or alkaline earth        metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal        phosphonate, alkyl phosphonate, amine and quaternary ammonium;        and    -   k is zero or an integer of 1 to 4; k is zero or an integer of 1        to 3.

Preferred dihalo (BB) are those complying with formulae (S′-1) to(S′-3), as shown below:

wherein:

-   -   each of R, equal to or different from each other, is selected        from the group consisting of halogen, alkyl, alkenyl, alkynyl,        aryl, ether, thioether, carboxylic acid, ester, amide, imide,        alkali or alkaline earth metal sulfonate, alkyl sulfonate,        alkali or alkaline earth metal phosphonate, alkyl phosphonate,        amine and quaternary ammonium;    -   j′ is zero or is an integer from 0 to 4;    -   X and X′, equal to or different from each other, are        independently a halogen atom, preferably Cl or F.

More preferred dihalo (BB) are those complying with following formulaeshown below:

wherein X is as defined above, X is preferably Cl or F.

Preferred dihaloaryl compounds [dihalo (BB)] are 4,4′-difluorodiphenylsulfone (DFDPS) and 4,4′-dichlorodiphenyl sulfone (DCDPS).

According to certain embodiments, the monomer mixture, as detailedabove, comprises a dihaloaryl compound obtained by reaction of aprecursor dihaloaryl compound of formula (S), as detailed above, whereinX, X′ is Cl [precursor dihalo (B_(Cl)B_(Cl)), herein after] with atleast one fluorinating agent [“Halex” reaction, herein after].

For the purpose of the present invention, the term “fluorinating agent”is intended to denote all reactants that are capable of substituting afluorine atom for the chlorine atom in dihalo(B_(Cl)B_(Cl)), as detailedabove.

As non limitative examples of fluorinating agents useful in the presentinvention are alkali or alkaline earth metal fluorides, e.g. LiF, NaF,KF, CsF, tetramethyl ammonium fluoride or tetrabutylammonium fluoride(TBAF), NH₄F or amine hydro fluorides, or the respective HF adducts.Preferred fluorinating agents are KF and CsF.

The amount of said fluorinating agent used, when expressed by the ratioof the equivalents of fluorine group (F) per equivalent of chlorinegroup (Cl) [eq. (F)/eq. (Cl)] ranges from 8.0 to 0.5, preferably from 6to 1, and more preferably from 4 to 1.5, being understood that abovementioned chlorine group equivalents are comprehensive of those of thedihalo(B_(Cl)B_(Cl)). Very good results have been obtained with a ratioof eq. (F)/eq. (Cl) of 2.

The “Halex” reaction can be carried out in a separate step prior to thepolymerization step or “in situ” during the polymerization step.

Preferably, the “Halex” reaction is carried out “in situ” as such thatthe reaction mixture including the solvent mixture comprising the polaraprotic solvent, the alkali metal carbonate and the monomer mixture, asdescribed above, further comprises the at least one fluorinating agent.

In another embodiment, the “Halex” reaction can be carried out in aseparate step wherein the precursor dihalo (B_(Cl)B_(Cl)), as detailedabove, undergoes a chlorine-fluorine exchange reaction in a separatestep thereby providing a mixture of Halex products. This being said, itis understood by the skilled in the art that said mixture of Halexproducts can suitably be used as monomers of the monomer mixture, asdetailed above, in the process of the present invention, as detailedabove.

If desired, the mixture of Halex products can be further purified bytechniques known in the art such as notably distillation, columnchromatography, crystallization, solid support chemistry, ion exchangechromatography, and the like.

Said mixture of Halex products comprises in general the unreactedprecursor dihalo (B_(Cl)B_(Cl)), as detailed above, the fullyfluorinated dihalo (BB), wherein X and X′ is F [dihalo (B_(F)B_(F))herein after] and the chlorofluoro dihalo (BB), wherein X and X′different from each other, are independently Cl or F.

The mixture of Halex products comprises the dihalo (B_(F)B_(F))advantageously in an amount of at least 70% by weight (wt. %),preferably of at least 80 wt. %, more preferably of at least 85 wt. %and most preferably of at least 90 wt. %.

If desired, the precursor dihalo (B_(ci)B_(ci)), as detailed above, arecompletely converted to the dihalo (B_(F)B_(F)).

The “Halex” reaction can be performed in the presence of a solvent.Solvents that may be suitable for the “Halex” reaction of this inventionare dimethylsulfoxide, dimethylsulfone, diphenylsulfone,diethylsulfoxide, diethylsulfone, diisopropylsulfone,tetrahydrothiophene-1,1-dioxide (commonly called tetramethylene sulfoneor sulfolane) and tetrahydrothiophene-1-monoxide and mixtures thereof.Very good results have been obtained with sulfolane ordimethylsulfoxide.

The “Halex” reaction is advantageously performed at a temperature equalto or higher than 150° C., preferably equal to or higher than 165° C.and more preferably equal to or higher than 200° C.

If desired, the “Halex” reaction is carried out in the presence of aphase transfer catalyst.

As non limitative examples of phase transfer catalysts useful in thepresent invention are phosphazenium salts such as notably(1,1,1,3,3,3-Hexakis(dimethylamino)diphosphazeniumtetrafluoroborate)-phosphazenium salt; crown ethers such as notably18-crown-6 and 12-crown-4, dibenzo-18-crown-6 or dibenzo-12-crownether-4; cryptands such as cryptand[2.2.2]; tetramethyl ammoniumfluoride or tetrabutylammonium fluoride (TBAF).

According to certain embodiments, unequal reactivity of hydroxyl groupsof 1,4:3,6-dianhydrohexitol may be used to generate in a first reactionstep of the process of the invention a bio-hydroxyl-halo compound (AB);typical examples of these bio-hydroxyl-halo compounds (AB) are thoseobtained by partial reaction of the isosorbide and/or the isoidide,typically having formulae:

wherein:

-   -   each of R′, equal to or different from each other, is selected        from the group consisting of halogen, alkyl, alkenyl, alkynyl,        aryl, ether, thioether, carboxylic acid, ester, amide, imide,        alkali or alkaline earth metal sulfonate, alkyl sulfonate,        alkali or alkaline earth metal phosphonate, alkyl phosphonate,        amine and quaternary ammonium; j′ is zero or is an integer from        0 to 4 and X and X′, equal to or different from each other, are        independently a halogen atom, preferably Cl or F.

Among dihaloaryl compound [dihalo (B′B′)] different from dihalo (BB)mention can be notably made of dihalobenzoid compound [dihalo (B′B′)] offormula:

wherein:

-   -   each of R, equal to or different from each other, is selected        from the group consisting of halogen, alkyl, alkenyl, alkynyl,        aryl, ether, thioether, carboxylic acid, ester, amide, imide,        alkali or alkaline earth metal sulfonate, alkyl sulfonate,        alkali or alkaline earth metal phosphonate, alkyl phosphonate,        amine and quaternary ammonium;    -   j is zero or is an integer from 1 to 4;    -   X and X′, equal to or different from each other, are        independently a halogen atom, preferably Cl or F.

Preferred dihalobenzoid compound [dihalo (B′B′)] are4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone and4-chloro-4′-fluorobenzophenone, with 4,4′-difluorobenzophenone beingparticularly preferred.

Among dihydroxyl compounds [diols (A′A′)] different from diol (AA), asabove detailed, mention can be of compounds of formula (O):

HO-Ar⁵-(T′-Ar⁶)_(n)—O—H   formula (O)

wherein:

-   -   n is zero or an integer of 1 to 5;    -   each of Ar^(y) and Ar⁶, equal to or different from each other        and at each occurrence, is an aromatic moiety of the formula:

wherein:

-   -   each R_(s) is independently selected from the group consisting        of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether,        carboxylic acid, ester, amide, imide, alkali or alkaline earth        metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal        phosphonate, alkyl phosphonate, amine and quaternary ammonium;        and    -   k is zero or an integer of 1 to 4; k′ is zero or an integer of 1        to 3; -T′ is a bond or a divalent group optionally comprising        one or more than one heteroatom; preferably T is selected from        the group consisting of a bond, —SO₂—, —CH₂—, —C(O)—, —C(CH₃)₂—,        —C(CF₃)₂—, —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—, and a group of        formula:

Among preferred dihydroxyl compounds [diols (A′A′)] different from diol(AA), as above detailed, suitable for being used in the process of thepresent invention, mention may be notably made of the followingmolecules:

Among hydroxyl-halo compound [hydro-halo (A′B′)] different frombio-hydroxyl-halo compound (AB), as above detailed, mention can be ofcompounds of any of formulae

-   -   each of R, equal to or different from each other, is selected        from the group consisting of halogen, alkyl, alkenyl, alkynyl,        aryl, ether, thioether, carboxylic acid, ester, amide, imide,        alkali or alkaline earth metal sulfonate, alkyl sulfonate,        alkali or alkaline earth metal phosphonate, alkyl phosphonate,        amine and quaternary ammonium;    -   T*, equal to or different from each other at each occurrence, is        independently a bond or a divalent group optionally comprising        one or more than one heteroatom; preferably T* is selected from        the group consisting of a bond, —SO₂—, —CH₂—, —C(O)—, —C(CH₃)₂—,        —C(CF₃)₂—, —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—;    -   j is zero or is an integer from 1 to 4;    -   X and X′, equal to or different from each other, are        independently a halogen atom, preferably Cl or F.

According to all embodiments of the present invention, the diol (AA) anddihalo (BB) and all other optional components (e.g. diol (A′A′), dihalo(B′B′) and hydro-halo (A′B′)) are dissolved or dispersed in a solventmixture comprising a polar aprotic solvent.

If desired, an additional solvent can be used together with the polaraprotic solvent which forms an azeotrope with water, whereby waterformed as a by-product during the polymerization may be removed bycontinuous azeotropic distillation throughout the polymerization.

The by-product water and carbon dioxide possibly formed during thepolymerization can alternatively be removed using a controlled stream ofan inter gas such as nitrogen or argon over and/or in to the reactionmixture in addition to or advantageously in the absence of anazeotrope-forming solvent as described above.

For the purpose of the present invention, the term “additional solvent”is understood to denote a solvent different from the polar aproticsolvent and the reactants and the products of said reaction.

As polar aprotic solvents, sulphur containing solvents known andgenerically described in the art as dialkyl sulfoxides anddialkylsulfones wherein the alkyl groups may contain from 1 to 8 carbonatoms, including cyclic alkyliden analogs thereof, can be mentioned.Specifically, among the sulphur-containing solvents that may be suitablefor the purposes of this invention are dimethylsulfoxide,dimethylsulfone, diphenylsulfone, diethylsulfoxide, diethylsulfone,diisopropylsulfone, tetrahydrothiophene-1, 1-dioxide (commonly calledtetramethylene sulfone or sulfolane) and tetrahydrothiophene-1-monoxideand mixtures thereof.

Very good results have been obtained with sulfolane.

Nitrogen-containing polar aprotic solvents, including dimethylacetamide,dimethylformamide and N-methyl pyrrolidone (i.e., NMP) and the like havebeen disclosed in the art for use in these processes, and may also befound useful in the practice of this invention. Very good results havebeen obtained with NMP.

The additional solvent that forms an azeotrope with water will generallybe selected to be inert with respect to the monomer components and polaraprotic solvent. Suitable azeotrope-forming solvents for use in suchpolymerization processes include aromatic hydrocarbons such as benzene,toluene, xylene, ethylbenzene, chlorobenzene and the like.

The azeotrope-forming solvent and polar aprotic solvent are typicallyemployed in a weight ratio of from about 1: 10 to about 1:1, preferablyfrom about 1:5 to about 1:3.

The alkali metal carbonate is preferably sodium carbonate, potassiumcarbonate, rubidium carbonate and cesium carbonate. Sodium carbonate andespecially potassium carbonate are preferred. Mixtures of more than onecarbonates can be used, for example, a mixture of sodium carbonate orbicarbonate and a second alkali metal carbonate or bicarbonate having ahigher atomic number than that of sodium.

The amount of said alkali metal carbonate used, when expressed by theratio of the equivalents of alkali metal (M) per equivalent of hydroxylgroup (OH) [eq. (M)/eq. (OH)] ranges from 1.3 to 4.0, preferably from1.4 to 3, and more preferably from about 1.5 to 2.5, being understoodthat above mentioned hydroxyl group equivalents are comprehensive ofthose of the diol (AA), and, if present, of bio-hydroxyl-halo compound(AB), of diol (A′A′) and of hydro-halo (A′B′). Very good results havebeen obtained with a ratio of eq. (M)/eq. (OH) of 2.0.

The Applicant has surprisingly found that the use of an optimum amountof alkali metal carbonate allows reducing significantly the reactiontimes of the process of the present invention while avoiding usingexcessive amounts of alkali metal carbonate which leads to higher costsand more difficult polymer purifications.

The use of an alkali metal carbonate having an average particle size ofless than about 100 μm, preferably of less than about 50 μm isparticularly advantageous. The use of an alkali metal carbonate havingsuch a particle size permits the synthesis of the polymers to be carriedout at a relatively lower reaction temperature with faster reaction.

According to a preferred embodiment of the present invention, theprocess is carried out in a solvent mixture comprising a polar aproticsolvent at a total % solids from in a range from 32% -38% and a ratio ofeq. (M)/eq. (OH) of 2.0.

Generally, after an initial heat up period, the temperature of thereaction mixture will be maintained in a range of advantageously from80-240° C., preferably from 120 to 230° C.

The reaction time is typically from 2 to 20 hours, preferably from 3 to12 hours, most preferably from 4 to 6 hours.

According to certain embodiments, the polymer (b-PAES) preparedaccording to the process of the present invention, as mentioned above,includes any polymer of which more than 30% moles of the recurring unitsare recurring units (R_(b)) derived from (I) at least one diol (AA), asdetailed above and (II) at least dihalo (BB), as detailed above, beingreacted in substantially equimolecular amount and in the presence of analkali metal carbonate.

Preferred recurring units (R_(b)) are selected from the group consistingof those of formula (R_(b)-1) to (R_(b)-6) herein below:

wherein:

-   -   each R′ is independently selected from the group consisting of        halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether,        carboxylic acid, ester, amide, imide, alkali or alkaline earth        metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal        phosphonate, alkyl phosphonate, amine and quaternary ammonium;        and    -   j′ is zero or an integer of 1 to 4;    -   T is a bond or a divalent group optionally comprising one or        more than one heteroatom; preferably T is selected from the        group consisting of a bond, —CH₂—, —C(O)—, —C(CH₃)₂—, —C(CF₃)₂—,        —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—, and a group of formula:

The above recurring units of preferred embodiments (R_(b)-1), (R_(b)-2),(R_(b)-3), (R_(b)-4), (R_(b)-5) and (R_(b)-6), can be each present aloneor in admixture.

More preferred recurring units (R_(b)) are those of formula (R_(b)-1)and (R_(b)-4), optionally in combination with recurring units of formula(R_(b)-2), (R_(b)-3), (R_(b)-5) and (R_(b)-6).

Most preferred recurring units (R_(b)) are of formula (R_(b)-1),optionally in combination with recurring units of formula (R_(b)-2) and(R_(b)-3).

In recurring unit (R_(b)), the respective phenylene moieties mayindependently have 1,2-, 1,4- or 1,3-linkages to the other moietiesdifferent from R′ in the recurring unit. Preferably, said phenylenemoieties have 1,3- or 1,4-linkages, more preferably they have1,4-linkage. Still, in recurring units (R_(b)), j′ is at each occurrencezero, that is to say that the phenylene moieties have no othersubstituents than those enabling linkage in the main chain of thepolymer.

According to certain embodiments, the polymer (b-PAES), as preparedaccording to the process of the present invention which comprisesadditionally reacting of a least one diol (A′A′) different from diol(AA), as detailed above; at least one dihalo (B′B′) different fromdihalo (BB), as detailed above; and at least one hydro-halo (A′B′) asdetailed above, comprises in addition to recurring units (R_(b)), asdetailed above, recurring units (R_(c)) comprising a Ar—SO₂—Ar′ group,with Ar and Ar′, equal to or different from each other, being aromaticgroups, said recurring units (R_(c)) generally complying with formulae(S1):

—Ar⁵-(T′-Ar⁶)_(n)—O—Ar⁷—SO₂—[Ar⁸-(T-Ar⁹)_(n)—SO₂]_(m)—Ar¹⁰—O—  (S1):

wherein:Ar⁵, Ar⁶, Ar⁷, Ar⁸, and Ar⁹, equal to or different from each other andat each occurrence, are independently a aromatic mono- or polynucleargroup;

-   -   T and T′, equal to or different from each other and at each        occurrence, is independently a bond or a divalent group        optionally comprising one or more than one heteroatom;        preferably T′ is selected from the group consisting of a bond,        —CH₂—, —C(O)—, —C(CH₃)₂—, —C(CF₃)₂—, —C(═CCl₂)—,        —C(CH₃)(CH₂CH₂COOH)—, —SO₂—, and a group of formula:

preferably T is selected from the group consisting of a bond, —CH₂—,—C(O)—, —C(CH₃)₂—, —C(CF₃)₂—, —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—, and agroup of formula:

-   -   n and m, equal to or different from each other, are        independently zero or an integer of 1 to 5;

Recurring units (R_(c)) can be notably selected from the groupconsisting of those of formulae (S1-A) to (S1-D) herein below:

wherein:

-   -   each of R′, equal to or different from each other, is selected        from the group consisting of halogen, alkyl, alkenyl, alkynyl,        aryl, ether, thioether, carboxylic acid, ester, amide, imide,        alkali or alkaline earth metal sulfonate, alkyl sulfonate,        alkali or alkaline earth metal phosphonate, alkyl phosphonate,        amine and quaternary ammonium;    -   j′ is zero or is an integer from 0 to 4;    -   T and T′, equal to or different from each other are a bond or a        divalent group optionally comprising one or more than one        heteroatom; preferably T′ is selected from the group consisting        of a bond, —CH₂—, —C(O)—, —C(CH₃)₂—, —C(CF₃)₂—, —C(═CCl₂)—,        —C(CH₃)(CH₂CH₂COOH)—, —SO₂—, and a group of formula:

preferably T is selected from the group consisting of a bond, —CH₂—,—C(O)—, —C(CH₃)₂—, —C(CF₃)₂—, —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—, and agroup of formula:

In recurring unit (R_(c)), the respective phenylene moieties mayindependently have 1,2-, 1,4- or 1,3-linkages to the other moietiesdifferent from R′ in the recurring unit. Preferably, said phenylenemoieties have 1,3- or 1,4-linkages, more preferably they have1,4-linkage. Still, in recurring units (R_(c)), j′ is at each occurrencezero, that is to say that the phenylene moieties have no othersubstituents than those enabling linkage in the main chain of thepolymer.

According to certain embodiments, the polymer (b-PAES), as preparedaccording to the process of the present invention which comprisesadditionally reacting of a least one diol (A′A′) different from diol(AA), as detailed above; at least one dihalo (B′B′) different fromdihalo (BB), as detailed above; and at least one hydro-halo (A′B′) asdetailed above, can thus comprise, in addition to recurring units(R_(b)), as detailed above, recurring units (R_(a)) comprising aAr—C(O)—Ar′ group, with Ar and Ar′, equal to or different from eachother, being aromatic groups, said recurring units (R_(a)) beinggenerally selected from the group consisting of formulae (J-A) to (J-O),herein below:

wherein:

-   -   each of R′, equal to or different from each other, is selected        from the group consisting of halogen, alkyl, alkenyl, alkynyl,        aryl, ether, thioether, carboxylic acid, ester, amide, imide,        alkali or alkaline earth metal sulfonate, alkyl sulfonate,        alkali or alkaline earth metal phosphonate, alkyl phosphonate,        amine and quaternary ammonium;    -   j′ is zero or is an integer from 0 to 4.

In recurring unit (R_(a)), the respective phenylene moieties mayindependently have 1,2-, 1,4- or 1,3-linkages to the other moietiesdifferent from R′ in the recurring unit. Preferably, said phenylenemoieties have 1,3- or 1,4-linkages, more preferably they have1,4-linkage.

Still, in recurring units (R_(a)), j′ is at each occurrence zero, thatis to say that the phenylene moieties have no other substituents thanthose enabling linkage in the main chain of the polymer.

As said, the polymer (b-PAES) comprises recurring units of formula R_(b)as above detailed in an amount of at least 30% moles, preferably 35%moles, more preferably 40% moles, even more preferably at least 50%moles, with respect to all recurring units of polymer (b-PAES).

According to certain preferred embodiments, more than 70, and morepreferably more than 85% moles of the recurring units of the polymer(b-PAES) are recurring units (R_(b)), as above detailed, the complementto 100% moles being generally recurring units (R_(a)), as abovedetailed, and/or recurring units (R_(c)), as above detailed.

Still more preferably, essentially all the recurring units of thepolymer (b-PAES) are recurring units (R_(b)), chain defects, or veryminor amounts of other units might be present, being understood thatthese latter do not substantially modify the properties of polymer(b-PAES). Most preferably, all the recurring units of the polymer(b-PAES) are recurring units (R_(b)). Excellent results were obtainedwhen the polymer (b-PAES) was a polymer of which all the recurring unitsare recurring units (R_(b)), as above detailed.

It is another object of the present invention to provide a polymer(b-PAES_(Cl)) prepared by the process according to the invention whereinsaid polymer (b-PAES_(Cl)) is derived from halo compounds, notablyincluding dihalo (BB) and/or in combination of optional dihalo (B′B′)compounds, as above detailed, wherein X and X′ is Cl.

It is another object of the present invention to provide a polymer(b-PAES_(F/Cl)) prepared by the process according to the inventionwherein said polymer (b-PAESp_(Cl)) is derived from a monomer mixturewhich is comprising a dihaloaryl compound obtained by the “Halexreaction”, as detailed above, of a precursor dihalo (B_(Cl)B_(Cl)), asdetailed above.

The polymer (b-PAES), prepared by the process of the present invention,has in general a weight averaged molecular weight of at least 20 000,preferably at least 30 000, more preferably at least 40 000.

The weight average molecular weight (M_(w)) and the number averagemolecular weight (M_(n)) can be estimated by gel-permeationchromatography (GPC) using ASTM D5296 calibrated with polystyrenestandards.

The weight average molecular weight (M_(w)) is:

$M_{w} = \frac{\sum\; {M_{i}^{2} \cdot N_{i}}}{\sum\; {M_{i} \cdot N_{i}}}$

The number average molecular weight (M_(n)):

${M_{n} = \frac{\sum\; {M_{i} \cdot N_{i}}}{\sum\; N_{i}}},$

andthe polydispersity index (PDI) is hereby expressed as the ratio ofweight average molecular weight (M_(w)) to number average molecularweight (M_(n)).

The polymer (b-PAES), as prepared according to the process of thepresent invention generally has a polydispersity index of less than 2.5,preferably of less than 2.4, more preferably of less than 2.2. Thisrelatively narrow molecular weight distribution is representative of anensemble of molecular chains with similar molecular weights andsubstantially free from oligomeric fractions, which might have adetrimental effect on polymer properties.

The polymer (b-PAES), as prepared according to the process of thepresent invention advantageously possesses a glass transitiontemperature of at least 200° C., preferably 210° C., more preferably atleast 220° C. Such high glass transition temperatures are advantageousfor extending temperatures range of use of the polymer (b-PAES).

Glass transition temperature (Tg) is generally determined by DSC,according to ASTM D3418.

In other words, the Applicant has succeeded in providing a process forthe manufacturing of a polymer (b-PAES) wherein the moieties of1,4:3,6-dianhydrohexitols have been successfully incorporated in thechain with no detrimental effect in polymerization reactivity, so thatan excellent material, with fully controlled structure is advantageouslyobtained.

Said process of the present invention, enables the preparation ofpolymers (b-PAES) which have advantageously extremely low levels ofinsolubles and extractibles, but still possessing increasedbio-compatibility due to the 1,4:3,6-dianhydrohexitols units, which havebeen found to be particularly useful for manufacturing membranes, inparticularly those intended for contact with body fluids and/or food andbeverages.

The polymer (b-PAES), as prepared according to the process of thepresent invention, can notably be used in medical, automotive,construction and aerospace applications as fibers, Further mention canbe made of automotive and aerospace applications as notably membranes,films and sheets, fibers, foams and three-dimensional moulded parts.

As per the processing, the polymer (b-PAES), as prepared according tothe process of the present invention, can be advantageously processedfor yielding all above mentioned articles by melt processing (includinginjection moulding, extrusion moulding, compression moulding), but alsoby solution processing, because of the solubility of the polymer(b-PAES).

It is another object of the present invention to provide a shapedarticle comprising the polymer (b-PAES), as prepared according to theprocess of the present invention.

Non limitative examples of shaped articles which can be manufacturedstarting from polymer (b-PAES), as prepared according to the process ofthe present invention, thereby using different processing technologiesare generally selected from the group consisting of melt processedfilms, solution processed films (porous and non porous films, includingsolution casted membranes, and membranes from solution spinning), meltprocess monofilaments and fibers, solution processed monofilaments,hollow fibers and solid fibers, and injection and compression moldedobjects.

Among membranes, the polymer (b-PAES), as prepared according to theprocess of the present invention, is particularly suitable formanufacturing membranes intended for contact with aqueous media,including body fluids; thus, shaped articles which can be manufacturedfrom said polymer (b-PAES) as above detailed are advantageouslymembranes for bioprocessing and medical filtrations, includinghemodialysis membranes, membranes for food and beverage processing,membranes for waste water treatment and membranes for industrial processseparations involving aqueous media.

From an architectural perspective, membranes manufactured from saidpolymer (b-PAES) as above detailed may be provided under the form offlat structures (e.g. films or sheets), corrugated structures (such ascorrugated sheets), tubular structures, or hollow fibers; as per thepore size is concerned, full range of membranes (non porous and porous,including for microfiltration, ultrafiltration, nanofiltration, andreverse osmosis) can be advantageously manufactured from said polymer(b-PAES); pore distribution can be isotropic or anisotropic.

Shaped articles manufactured from the polymer (b-PAES), as preparedaccording to the process of the present invention, can be, as abovementioned, under the form of films and sheets. These shaped articles areparticularly useful as specialized optical films or sheets, and/orsuitable for packaging.

Further, shaped articles manufactured from the polymer (b-PAES), asprepared according to the process of the present invention, can bethree-dimensional moulded parts, in particular transparent or colouredparts.

Among applications of use wherein such injection moulded parts can beused, mention can be made of healthcare applications, in particularmedical and dental applications, wherein shaped articles made from thepolymer (b-PAES), as prepared according to the process of the presentinvention, can advantageously be used for replacing metal, glass andother traditional materials in single-use and reusable instruments anddevices. Should the disclosure of any patents, patent applications, andpublications which are incorporated herein by reference conflict withthe description of the present application to the extent that it mayrender a term unclear, the present description shall take precedence.

EXAMPLES

The invention will be now described in more details with reference tothe following examples, whose purpose is merely illustrative and notintended to limit the scope of the invention.

General Description of the Preparation of the polymer (b-PAES)

To a clean 250 mL four-neck round bottom flask fitted with a mechanicalstirrer, Dean-Stark trap, condenser, and nitrogen inlet, was placed theisosorbide, the dihalo (BB) (4,4′-difluorodiphenyl sulfone (DFDPS) or4,4′-dichlorodiphenyl sulfone (DCDPS)), and potassium carbonate followedby the polar aprotic solvent (sulfolane or dimethylsulfoxide (DMSO)) andoptionally the additional solvent (e.g. toluene). A slight stream ofnitrogen was applied above the reaction mixture through one of the necksof the flask with an exit through a bubbler above the condenser. Thereaction mixture was stirred with an overhead mechanical agitator andwarmed using an oil bath controlled at the appropriate temperature. Thebath temperature increased from 21° C. to the appropriate temperatureover about 30-60 minutes and held at the reaction temperature for adesired period of time When the mixture became viscous and moredifficult to stir, the reaction mixture was diluted with NMP, cooled to<100° C., and the mixture poured in to a Waring blender containing 500mL of a 50/50 v/v mixture of water and methanol. The resulting off-whiteporous solid was then isolated by filtration, and washed three times inthe Waring blender with hot DI water (˜90° C.) and twice with methanolwith filtration between each wash. The resulting porous, off-whitepolymer solid was dried in a vacuum oven overnight at 100° C. Thepolymer solid was further analyzed by viscosity measurements, GPC andDSC to determine the molecular weight, and thermal properties (allreaction conditions and results are summarized in Tables 1 and 2).

The Following Characterizations Carried out on the Materials of theExamples are Indicated Hereinafter: Viscosity Measurements

Intrinsic viscosity (IV) of the polymers (b-PAES) were measured insolvent mixture: CH₂Cl₂/trifluoroacetic acid in a volume ratio of 9/1,at a polymer concentration of 0.2 g/100 ml at 20° C. using aCannon-Fenske viscometer tube (No. 50) according to the procedure asdescribed by Kricheldorf and Chatti in High Performance Polymers, 2009,21, 105-118, which is hereby incorporated by reference in its entirety.

Comparative Example 1

Said comparative example corresponds to an example described byKricheldorf and Chatti in High Performance Polymers, 2009, 21, 105-118,the general procedure of the polycondensation reaction is described onpage 106, paragraph 2.2 and in Table 2, Expt.no. 3. For the total %monomers value, it was necessary to convert the mole values values ofIsosorbide (30.0 mmol) and DFDPS (30.6 mmol) into weight values, being4.4 g and 7.8 g, respectively, the corresponding weight of DMSO andtoluene were calculated using a density value of 1.1 g/mL for DMSO and0.87 g/mL for toluene, the corresponding weights are shown in Table 1.All reaction conditions and results are summarized in Table 1.

Examples 2 9; 11-13, 15, 16 and C10, C14 and C17

All these examples are carried out according to the general procedureand the corresponding reaction conditions are shown in Table 1 and 2.

Examples C1, 2 and 3, as shown in Table 1 were carried out by using4,4′-difluorodiphenyl sulfone (DFDPS) as dihalo (BB).

All other examples were carried out by using 4,4′-dichlorodiphenylsulfone (DCDPS) as dihalo (BB).

TABLE 1 Examples N^(o) C1^(a) 2 3 4 5 6 7 8 9 dihalo (BB DFDPS DCDPSReaction parameters: Solvent DMSO DMSO Sulfolane Sulfolane SulfolaneSulfolane Sulfolane Sulfolane Sulfolane Cosolvent toluene toluene nonenone none none none none none Cosolvent/solvent (v/v) 0.2 0.7 — — — — —— — Weight of solvent (g) 127.4 38.8 258.7 56.4 30.2 23.17 18.0 9.0 15.0Weight isosorbide (g) 4.4 5.8 45.0 4.1 4.1 4.1 4.1 2.0 4.1 Weight dihalo(BB) 7.8 10.4 80.0 8.0 8.1 8.0 8.0 4.1 8.0 Molar Ratio 1.02 1.02 1.021.0 1.0 1.0 1.0 1.0 1.0 dihalo (BB)/isosorbide Molar Ratio 1.05 1.501.50 2.0 2.0 2.0 2.0 2.0 2.0 K₂CO₃/isosorbide Sum of the weight of all12.2 16.2 125.0 12.1 12.2 12.1 12.1 6.1 12.1 monomers (g) Total %monomers 8.7 29.5 32.5 17.7 28.8 34.3 40.2 40.4 44.6 Reactiontemperature (° C.) 135-140 175-180 210 210 210 210 210 210 210 Reactiontime (hr) 12 1.5 2.0 4.0 4.0 4.0 4.0 6.0 4.0 Polymer properties Inherentviscosity (dL/g)* 0.65^(b) 0.74^(b) 0.72^(b) — — — — 0.38^(b) — M_(w)(GPC) (kDa) — 102 101 24.6 41.4 42.7 55.1 58.0 50.3 T_(g) (° C.) (DSC,20° C./min) 245.5 241 241 210 219 215 225 234 226 ^(a)Said comparativeexample is an example described by Kricheldorf and Chatti in HighPerformance Polymers, 2009, 21, 105-118, see Table 2, Expt no. 3^(b)CH₂Cl₂/trifluoroacetic acid = 9/1 v/v, 20° C., 0.20 dL/g ^(c)1 hourpreheating at 160° C.

TABLE 2 Examples N^(o) 7 C10 11 12 13 C14 15 16 C17 dihalo (BB) DCDPSReaction parameters: Solvent Sulfolane Sulfolane Sulfolane SulfolaneSulfolane Sulfolane Sulfolane Sulfolane Sulfolane Cosolvent none nonenone none none none none none none Weight of solvent (g) 18.0 18.1 18.018.0 18.0 19.3 19.1 17.8 17.1 Weight isosorbide (g) 4.1 4.1 4.1 4.1 4.14.1 4.1 4.1 4.9 Weight dihalo (BB) 8.0 8.0 8.0 8.0 8.0 8.8 8.4 7.6 7.2Molar Ratio 1.0 1.0 1.0 1.0 1.0 0.90 0.95 1.05 1.10 dihalo(BB)/isosorbide Molar Ratio 2.0 1.2 1.5 1.75 3.0 2.0 2.0 2.0 2.0K₂CO₃/isosorbide Sum of the weight of all 12.1 12.1 12.1 12.1 12.1 12.912.5 11.7 12.1 monomers (g) Total % monomers 40.2 40.2 40.2 40.2 40.240.1 40.0 40.0 41.4 Reaction temperature (° C.) 210 210 210 210 210 210210 210 210 Reaction time (hr) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0Polymer properties Inherent viscosity (dL/g)* — — — — — 0.38^(a) — — —M_(w) (GPC) (kDa) 55.1 18.4 45.9 46.8 49.0 19.7 35.9 23.6 7.7 T_(g) (°C.) (DSC, 20° C./min) 225 180 220 216 225 198 214 202 164^(a)CH₂Cl₂/trifluoroacetic acid = 9/1 v/v, 20° C., 0.20 dL/g

Example 18 “Halex” Reaction of 4,4′-dichlorodiphenyl sulfone (DCDPS) asdihalo (B_(Cl)B_(Cl)) Providing a Mixture of Halex Products

A 50 ml-round bottom flask is charged with 1.0 g (3.484 mmol) DCDPS and2.1 g (13.94 mmol) CsF and 3.54 g sulfolane and heated with oil bath to210° C. The Halex reaction was carried out at this temperature for 24hours. After completion of the reaction, a small sample of the reactionmixture was diluted with dichloromethane, and treated with activatedcarbon to remove color bodies and the dichloromethane solution wasremoved by a rotavapor. The residual product was analyzed by GC. GCanalysis of the isolated product showed 90.8% of DFDPS, 6.7% of4-chloro-4′-fluoro-diphenyl sulfone and 2.5% of DCDPS starting material.

Example 19 “Halex” Reaction of 4,4′-dichlorodiphenyl Sulfone (DCDPS) asDihalo (B_(Cl)B_(Cl)) Providing a Mixture of Halex Products

A 50 ml-round bottom flask is charged with 2.0 g (6.96 mmol) DCDPS and2.1 g (13.94 mmol) CsF and 5.0 g sulfolane and heated with oil bath to210° C. The Halex reaction was carried out at this temperature for 24hours. After completion of the reaction, a small sample of the reactionmixture was diluted with dichloromethane, and treated with activatedcarbon to remove color bodies and the dichloromethane solution wasremoved by a rotavapor. The residual product was analyzed by GC. GCanalysis of the isolated product showed 90.5% of DFDPS and 9.5% of4-chloro-4′-fluoro-diphenyl sulfone.

Example 20 “Halex” Reaction of 4,4′-dichlorodiphenyl Sulfone (DCDPS) asDihalo (B_(Cl)B_(Cl)) Providing a Mixture of Halex Products in thePresence of a PTC

To a 3-neck 1L-round bottom flask equipped with a mechanical stirrerwith a nitrogen inlet and outlet, was charged 253.33 g (0.8823 mol),DCDPS, 205.0 g (3.529 mol), anhydrous KF 10.86 g (4.411 mmol),18-crown-6, and 406 g sulfolane. The mixture was gradually heated to210° C. in oil bath and the reaction was carried out at this temperaturefor 20 hours. After completion of the reaction, the reaction mixture wasfiltered by a high pressure filter to remove an excessive salt anddichloromethane was added to the filtered solution. Later DI water wasadded to dichloromethane and organic layer was separated. Then theorganic layer washed again with DI water to remove residual sulfolane.To the collected organic layer, some activated carbon was added toremove color and small amount of MgSO₄ was added to remove any traces ofwater. The solution was filtered and dichloromethane was removed by arotavapor. GC analysis of the isolated product showed 88.1% of DFDPS and11.9% of chloro-fluoro-diphenyl sulfone.

Example 21 Preparation of the Polymer (b-PAES_(F/Cl)) by using a Mixtureof Halex Products

In a 250-ml, 4-neck round bottom flask is equipped with a mechanicalstirrer, a nitrogen inlet and outlet, thermocouple and a Dean-Starktrap, was charged 15.0 g isosorbide, 26.66 g Halex product of example 20(88.1% of DFDPS and 11.9% of F-Cl-DPS), 21.28 g K₂CO₃, and 110.85 gsulfolane were charged. The mixture was slowly heated to 210° C. and thepolymerization carried out at this temperature. After 5 hrs reactiontime, the polymerization solution became very viscous and the reactionwas stopped. The reaction mixture was cooled to 140° C., NMP solvent wasadded to dilute the solution and the polymerization slurry mixture wasfiltered. Later the filtered solution was poured into methanol/watermixture to precipitate the polymer and the isolated polymer was washedwith hot water three times. The polymer subjected to a final wash withpure methanol and polymer powder was dried under vacuum at 90° C. Thepolymer was characterized by GPC and DSC. The GPC analysis revealed thatthe polymer powder has an Mw=74661 Da and the DSC showed the polymer tohave a Tg of 227° C.

Example 22 Preparation of the Polymer (b-PAES_(F/Cl)) by using an“in-situ” Halex Reaction

A 250-ml, 4-neck round bottom flask is equipped with a mechanicalstirrer, nitrogen inlet and outlet, thermocouple and a Dean-Stark and5.0 g (34.21 mmol) isosorbide, 9.923 g (34.56 mmol) DCDPS, 9.45 g (68.42mmol) K₂CO₃, 3.969 g (68.42 mmol) KF and 28.75 g sulfolane were charged.The mixture was slowly heated to 210° C. and the polymerization carriedout at this temperature. The reaction mixture was cooled to 140° C., NMPsolvent was added to dilute the solution and the polymerization slurrymixture was filtered. Later the filtered solution was poured intomethanol/water mixture to precipitate the polymer and the isolatedpolymer was washed with hot water three times. The polymer subjected toa final wash with pure methanol and polymer powder was dried undervacuum at 90° C. The polymer was characterized by GPC and DSC. The GPCanalysis revealed that the polymer powder has an Mw=37355 Da and DSCshowed Tg of 219° C.

1-16. (canceled)
 17. A process for manufacturing a poly(arylethersulfone)polymer, polymer (b-PAES), comprising reacting in a solventmixture, the solvent mixture comprising a polar aprotic solvent, and inthe presence of an alkali metal carbonate, a monomer mixture comprising:at least one 1,4:3,6-dianhydrohexitol, diol (AA), selected from thegroup consisting of isosorbide (1), isomannide (2), and isoidide (3):

at least one dihaloaryl compound, dihalo (BB), of formula (S):X—Ar—SO₂—[Ar²-(T-Ar³)_(n)—SO₂]_(m)—Ar⁴—X′  formula (S) wherein n and m,equal to or different from each other, are independently zero or aninteger of 1 to 5; X and X′, equal to or different from each other, arehalogens selected from F, CI, Br, and I; each of Ar¹, Ar², Ar³ and Ar⁴,equal to or different from each other and at each occurrence, is anaromatic moiety; T is a bond or a divalent group optionally comprisingone or more than one heteroatom; optionally, at least one dihydroxylcompound, diol (A′A′), different from the diol (AA); optionally, atleast one dihaloaryl compound, dihalo (B′B′), different from the dihalo(BB); optionally, at least one hydroxyl-halo compound, hydro-halo(A′B′); with the proviso that the overall amount of halo-groups andhydroxyl-groups of the monomers of the monomer mixture is substantiallyequimolecular, so as to obtain the polymer (b-PAES), and wherein thereaction is carried out at a total % monomer mixture concentration,total % monomers, equal to or more than 15% and less than 70%, withrespect to the combined weight of monomer mixture and solvent mixture.18. The process according to claim 17, wherein the dihalo (BB) are thosehaving formulae (S′-1) to (S′-3):

wherein: each of R′, equal to or different from each other, is selectedfrom the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl,ether, thioether, carboxylic acid, ester, amide, imide, alkali oralkaline earth metal sulfonate, alkyl sulfonate, alkali or alkalineearth metal phosphonate, alkyl phosphonate, amine, and quaternaryammonium; j′ is zero or is an integer from 0 to 4; and X and X′, equalto or different from each other, are independently a halogen atom. 19.The process according to claim 17, wherein the monomer mixture comprisesa dihaloaryl compound obtained by reaction of a precursor dihaloarylcompound of formula (S), wherein X, X′ is CI, precursor dihalo(B_(Cl)B_(Cl)), with at least one fluorinating agent.
 20. The processaccording to claim 17, wherein the monomer mixture contains at least onediol (A′A′) different from the diol (AA), the diol (A′A′) is selectedfrom the group consisting of compounds of formula (O):HO-Ar⁵-(T′-Ar⁶)_(n)—O—H   formula (O) wherein: n is zero or an integerof 1 to 5; each of AO and Ar⁶, equal to or different from each other andat each occurrence, is an aromatic moiety of formual:

wherein: each R_(s) is independently selected from the group consistingof halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylicacid, ester, amide, imide, alkali or alkaline earth metal sulfonate,alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkylphosphonate, amine, and quaternary ammonium; and k is zero or an integerof 1 to 4; k′ is zero or an integer of 1 to 3; and T′ is a bond or adivalent group optionally comprising one or more than one heteroatom.21. The process according to claim 17 , wherein the monomer mixturecomprises at least one dihalo (B′B′) different from the dihalo (BB), thedihalo (B′B′) is of formula:

wherein: each of R, equal to or different from each other, is selectedfrom the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl,ether, thioether, carboxylic acid, ester, amide, imide, alkali oralkaline earth metal sulfonate, alkyl sulfonate, alkali or alkalineearth metal phosphonate, alkyl phosphonate, amine, and quaternaryammonium; j is zero or is an integer from 1 to 4; and X and X′, equal toor different from each other, are independently a halogen atom.
 22. Theprocess according to claim 17, wherein the polar aprotic solvent isselected from a group consisting of dimethylsulfoxide, dimethylsulfone,diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone,tetrahydrothiophene-1, 1-dioxide, tetrahydrothiophene-1-monoxide, andmixtures thereof.
 23. The process according to claim 17, wherein thetotal % monomers is in a range from 35% -42%.
 24. The process accordingto claim 17, wherein the overall amount of the hydroxyl-groups and thehalo-groups has a molar ratio of 0.95 to 1.05.
 25. The process accordingto claim 17, wherein the alkali metal carbonate is selected from thegroup consisting of sodium carbonate, potassium carbonate, rubidiumcarbonate, and cesium carbonate.
 26. The process according to claim 17,wherein the amount of the alkali metal carbonate ranges from 1.3 to 4.0,when expressed by a ratio of equivalents of alkali metal (M) perequivalent of hydroxyl group (OH) [eq. (M)/eq. (OH)].
 27. A polymer(b-PAES_(Cl)) prepared by the process according to claim 17, wherein thepolymer (b-PAES_(Cl)) is derived from halo compounds, including dihalo(BB) and/or in combination of optional dihalo (B′B′), wherein X and X′is Cl.
 28. A polymer (b-PAES_(Cl)) prepared by the process according toclaim
 17. 29. A shaped article manufactured from the polymer (b-PAES)prepared according to claim 17 selected from the group consisting ofmelt processed films, solution processed films, melt processmonofilaments and fibers, solution processed monofilaments, hollowfibers and solid fibers, and injection and compression molded objects.30. A shaped article manufactured from the polymer (b-PAES) preparedaccording to claim 17 selected from membranes for bioprocessing,membranes for medical filtrations, membranes for food and beverageprocessing, membranes for waste water treatment, and membranes forindustrial process separations involving aqueous media.
 31. A shapedarticle manufactured from the polymer (b-PAES) prepared according toclaim 17 selected from films and sheets.
 32. The process according toclaim 17, wherein the X and X′, equal to or different from each other,are halogens selected from CI and F.
 33. The process according to claim17, wherein T is selected from the group consisting of a bond, —CH₂—,—C(O)—, —C(CH₃)₂—, —C(CF₃)₂—, —C(═CCl₂)—, —C(CH₃)(CH₂CH₂COOH)—, and agroup of formula:


34. The process according to claim 17, wherein the alkali metalcarbonate is selected from sodium carbonate and potassium carbonate. 35.The shaped article according to claim 30, wherein the membrane formedical filtrations are hemodialysis membranes.
 36. A method formanufacturing a membrane, film, sheet, or three-dimensional moulded partcomprising processing the polymer (b-PAES) prepared by the process ofclaim 17 into the membrane, the film, the sheet, or thethree-dimensional moulded part.